CN1276936C - Styrene resin composition and process for producing the same - Google Patents
Styrene resin composition and process for producing the same Download PDFInfo
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- CN1276936C CN1276936C CNB038029499A CN03802949A CN1276936C CN 1276936 C CN1276936 C CN 1276936C CN B038029499 A CNB038029499 A CN B038029499A CN 03802949 A CN03802949 A CN 03802949A CN 1276936 C CN1276936 C CN 1276936C
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- branched chain
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
A styrene resin composition is provided which has a high molecular weight enabling a molded product obtained therefrom to have satisfactory strength, has a high melt mass-flow rate, high melt tension, and hence excellent moldability, and is less apt to gel during production, and a process for producing such a styrene resin composition. The styrene resin composition comprises a linear polystyrene having a weight average molecular weight of 200,000 to 350,000 and a multibranched polystyrene having a weight average molecular weight of 1,000,000 to 10,000,000, has an average molecular weight of 250,000 to 700,000, and a melt mass-flow rate (MFR) and melt tension (MT) which satisfy the following formulas (1) and (2) respectively: MFR>=45*exp(-0.1*Mw*10<-4>) (1) MT>=0.07Mw*10<-4>+1.8 (2).
Description
Background of invention
Invention field
The present invention relates to composition of styrene resin and a kind of method for preparing this composition of styrene resin that a kind of composition comprises linear polystyrene and higly branched chain polystyrene.Compare with the linear polystyrene with identical weight-average molecular weight, therefore good flowability when composition of styrene resin of the present invention has higher melt mass flow rate and moulding is to be adapted at the desirable formed material that uses in the multiple forming method.
Description of the Prior Art
Because styrene base resin shows good rigidity and dimensional stability, and production cost is low, therefore be widely used in moulding and use.In recent years, in many application, found the styrene base resin that improves intensity, though improve the molecular weight of styrene base resin is the effective ways that improve styrene base resin intensity, linear polystyrene for routine, the raising molecular weight causes the increase of melt viscosity, and the result obviously descends forming ability.
Adding softening agent is the typical method that the such forming ability of repacking descends, yet this can cause the decline of final resin molded product physical strength.Japan's unexamined patent application, openly NO.Sho 41-15911 discloses a kind of by giving the method example that the vinylbenzene branched structure is intended to head it off for the second time, wherein the introducing of branched structure is by using vinylbenzene and as the multifunctional peralcohol of polymerization starter, for example 2,2-two (4,4-di-t-butyl-peroxide-cyclohexyl) propane initiator is even use this method, the degree of branching only can be controlled at a lower level, is difficult to obtain gratifying higly branched chain structure.
Japanese unexamined patent, NO.Hei 7-166013 is disclosed for the first time, giving the polystyrene branched structure, and obtain in the trial of polyvinyl resin of high molecular and good forming ability, Japanese unexamined patent, for the first time openly to disclose a kind of weight-average molecular weight by following method preparation be 200 to NO.Hei 7-166013,000 to 2,000,000 polystyrene base co-polymer: by vinylbenzene and a kind of compound that contains at least two vinyl groups for example Vinylstyrene copolymerization and branched structure introduced in the polystyrene chain contain at least.Disclose the polystyrene-based copolymer sheet that forms and revealed good forming ability, although because it is easy to gel in polymerization process, be difficult to industrial production, and because other contains the compound limited amount of vinyl at least, so be difficult to reach the significantly improving of physicals of rosin products.
In another of the polyvinyl resin that obtains high molecular and good forming ability attempted, Japanese unexamined patent, for the first time openly NO.Hei 316261 discloses the mixture of the linear polystyrene that a kind of star-like side chain polystyrene that is generated by anionoid polymerization and radical polymerization generates, and report can under the condition that does not have hardness and loss of thermal resistance, prepare have good fluidity, physical strength and the good composition of styrene resin of forming ability.Yet, owing to use anionoid polymerization, thereby need complicated control, make this method be not suitable for industrial production.
Summary of the invention
Summary of the invention
The purpose of this invention is to provide a kind of composition of styrene resin, described composition has the high molecular that the moulding product that can make acquisition has gratifying intensity, have high melt mass flow rate, high melt tension, therefore has good forming ability, and be not easy to gel aborning, and a kind of method for preparing this composition of styrene resin is provided.
The result of thoroughgoing and painstaking research as being intended to achieve the above object, the present inventor has found a kind of composition of styrene resin, comprise a kind of by higly branched chain macromonomer and the styrene copolymerized higly branched chain polystyrene that obtains and a kind of linear polystyrene, has good melt tension (MT), high melt mass flow rate (MFR) also is provided simultaneously, good forming ability, good anti-gelation, they can finish the present invention thus.
Thereby, the invention provides a kind of composition of styrene resin, it comprises that a kind of weight-average molecular weight is 200,000 to 350,000 linear polystyrene and a kind of weight-average molecular weight are 1,000,000 to 10,000,000 higly branched chain polystyrene, melt mass flow rate (MFR) and melt tension (MT) that it has 250,000 to 700,000 weight-average molecular weight and satisfies following formula (1) and (2) respectively:
MFR 〉=45 * exp (0.1 * Mw * 10
-4) (1) (wherein, MFR and Mw represent the melt mass flow rate and the weight-average molecular weight of composition of styrene resin respectively),
MT 〉=0.07Mw * 10
-4+ 1.8 (2) (wherein, MT and Mw represent the melt tension and the weight-average molecular weight of composition of styrene resin respectively).
In addition, the present invention also provides a kind of method for preparing composition of styrene resin recited above, this method comprises: make (A) higly branched chain macromonomer and (B) vinylbenzene carry out radical polymerization, described higly branched chain macromonomer (A) comprises branched structure that contains electron withdrawing group and tertiary carbon atom and the two keys that directly are connected with aromatic ring, in described tertiary carbon atom, three keys except that a key that is connected with electron withdrawing group all are connected with other carbon atom.
In addition, the invention provides the method for described composition of styrene resin above the preparation, the method that wherein prepares the higly branched chain polystyrene is carried out radical polymerization by (A) higly branched chain macromonomer and (B) vinylbenzene and is prepared, described higly branched chain macromonomer comprises to contain and is selected from ester bond, the branched structure of the repeated structural unit in ehter bond and the amido linkage and at the two keys of a terminated.
The invention provides a kind of composition of styrene resin, its moulding product with the acquisition of making has the high weight-average molecular weight of gratifying intensity, the conventional linear polystyrene identical with weight-average molecular weight compared, have higher melt mass flow rate and melt tension, therefore excellent forming ability is provided, and when moulding, be difficult for gelling, and a kind of method for preparing this composition of styrene resin is provided.
Description of drawings
Fig. 1 is by AB
2The synoptic diagram of the branched structure of the higly branched chain macromonomer of type monomer derived.
Fig. 2 is the GPC chromatogram of the resin combination of embodiment 2.Transverse axis is represented retention time, and the longitudinal axis is represented peak strength
Figure 3 shows that the weight-average molecular weight of embodiment 1 to 10 and comparative example 1 to 3 and the graph of a relation of MFR value.Small circle is represented the result of embodiment, and square is represented the result of comparative example, and curve representation is represented weight-average molecular weight and the MFR value relation based on following formula:
(MFR＝45×exp(-0.1×Mw×10
-4))
Detailed Description Of The Invention
It below is the more detailed description of resin combination of the present invention.
Composition of styrene resin of the present invention comprises the highly branched chain polystyrene that obtained with the highly branched chain macromonomer of many pairs of keys and styrene polymerization by molecular end and the linear polystyrene of preparation simultaneously. Branched structure for the highly branched chain polystyrene that contains in the composition of styrene resin of the present invention is not particularly limited, although preferred two kinds of such highly branched chain polystyrene, a kind of have contain electron-withdrawing group be connected with tertiary carbon atom branched structure be connected the two keys that are connected with aromatic ring, in tertiary carbon atom, except with key that electron-withdrawing group is connected three keys all be connected with other carbon atom, another kind comprises the branched structure that contains in the constitutional repeating unit that is selected from ehter bond, ester bond and the amido link.
The branched structure of highly branched chain polystyrene derived from styrene copolymerized highly branched chain macromonomer. By per 1 gram highly branched chain polystyrene, the electron-withdrawing group content of the branched structure of the highly branched chain polystyrene that contains in composition of styrene resin of the present invention typically is 2.5 * 10-4To 5.0 * 10-1MM, be preferably 5.0 * 10-4To 5.0 * 10-2MM.
For highly branched chain macromonomer of the present invention except with not special restriction the more side chain, a preferred structure example is: such highly branched chain macromonomer, namely in an independent molecule, its comprise contain electron-withdrawing group be connected with tertiary carbon atom branched structure be connected the two keys that are connected with aromatic ring, in tertiary carbon atom, except a key that is connected with electron withdraw group, three keys all are connected with other carbon atom. This highly branched chain macromonomer is by AB2The macromonomer of hyperbranched (hyperbranched) of monomer derived, and it has and is similar to the branched structure that Fig. 1 schematically shows.
This branched structure can be by the easily preparation with the nucleophilic substitution of the active methylene group of the electron withdraw group that is connected. The example of electron withdraw group comprises-CN ,-NO2，-CONH
2，-CON(R)
2，
-SO
2CH
3, and-P (=O) (OR)2, and the methylene that is connected with electron-withdrawing group directly with situation that aromatic ring or carbonyl are connected under, the then active further increase of methylene.
Employed highly branched chain macromonomer example is a kind of highly branched chain macromonomer among the present invention, and it contains the side chain that comprises with the repetitive of the expression of the general formula (I) shown in following:
General formula (I)
[wherein, Y1Expression is selected from-CN-NO2，-CONH
2，-CON(R)
2，-SO
2CH
3, and-P (=O) (OR)2Electron-withdrawing group in (wherein R represents alkyl or aryl), Y2The expression arlydene ,-O-CO-or-NH-CO-, and Z represents to be selected from-(CH2)
nO-，-(CH
2CH
2O)
n-，-(CH
2CH
2CH
2O)
n-in group, if Y2For-O-CO-or-NH-CO-, then Z represents-(CH2)
n-，-(CH
2)
nAr-，-(CH
2)
nO-Ar-，
-(CH
2CH
2O)
n-Ar-, or-(CH2CH
2CH
2O)
n-Ar-(wherein Ar represents aryl)].
For example, Y
2Also can be the arylidene that is selected from formula as follows:
In these, Y wherein
1Be-CN and Y
2The structure that is phenylene is preferred.At Y
2Be under those situations of phenylene, though have no particular limits for the link position of Z, any in ortho position, a position, the contraposition all is acceptable, and contraposition is preferred.In addition, be not particularly limited for the number of repeating unit in the Z group, though from guaranteeing vinylbenzene solvability angle, 1 to 12 value is preferred, and 2 to 10 value more wishes to obtain.
The aforesaid higly branched chain macromonomer that contains branched structure can be prepared by following method in the presence of a kind of basic cpd:
(i) pass through AB
2The type monomer carry out nucleophilic substitution reaction prepare a kind of higly branched chain from the polycondensate of condensed type as precursor, described AB
2The type monomer contains active methylene radical and is used for the leaving group of the nucleophilic substitution reaction of this active methylene radical in individual molecule, then
(ii) make to be retained in the polycondensate unreacted methylene radical or methyne and a kind of compound and to carry out nucleophilic substitution reaction, described compound comprises the two keys that directly are connected with aromatic ring and is used for the leaving group of the nucleophilic substitution reaction of this active methylene radical in individual molecule.
In describing above, the leaving group that is used for the nucleophilic substitution reaction of active methylene radical be meant the halogen atom that is connected with tertiary carbon atom or-OS (=O)
2(wherein R represents alkyl or aryl), and specific examples comprises bromine atoms, chlorine atom, methylsulfonyl oxygen base or benzene mesyloxy.
Preferred highly basic such as sodium hydroxide or potassium hydroxide are basic cpd, and the form with the aqueous solution is used in reaction.
The AB that in individual molecule, contains the active methylene radical and the leaving group of the nucleophilic substitution reaction that is used for this active methylene radical
2Type monomer example comprises: halogenated phenalkyloxy-acetonitrile, as bromo oxyethyl group-phenylacetonitrile and chloro methyl benzyloxy-phenylacetonitrile with contain phenylacetonitrile such as benzene mesyloxy-two (the ethylene oxide)-benzyl cyanide and Oxybenzene methylsulfonyl-two (the vinyloxy group)-phenylacetonitrile of benzene mesyloxy.
The expression example that comprises the direct two keys that are connected with aromatic ring and the compound of the leaving group of the nucleophilic substitution reaction that is used for this active methylene radical in individual molecule comprises chloro vinyl toluene and bromomethyl vinylbenzene.
Above-mentioned reaction (i) is used for synthesizing the polycondensate as precursor, and reaction is (ii) introduced precursors by two keys that will directly be connected with aromatic ring and synthesized the higly branched chain macromonomer.Reaction (i) (ii) can be carried out separately and one after the other with reaction, also can carry out simultaneously in same reaction system.The molecular weight of higly branched chain macromonomer can be controlled by the example of comparing that changes monomer and basic cpd.
Another example of employed preferred higly branched chain macromonomer is among the present invention: a kind of like this higly branched chain macromonomer, it comprises to contain and is selected from ester bond, the branched structure of the repeated structural unit in ehter bond and the amido linkage and at the two keys of a terminated.
Comprising ester bond is that the unitary higly branched chain macromonomer of repeating structure is the structure for preparing by following method: vinyl double bond such as vinyl or pseudoallyl are introduced the higly branched chain polyester polyol that contains molecular chain, in described molecular chain, the carbon atom adjacent with the carbonyl of the ester bond that forms molecular chain is tertiary carbon atom.Can be undertaken introducing these vinyl double bonds by esterification or addition reaction to the higly branched chain polyester polyol.
The example that the higly branched chain polyester polyol of the above-mentioned type can be purchased comprises then " Boltorn H20, H30 and the H40 " of Perstorp AB production.
Above-mentioned higly branched chain polyester polyol can contain substituting group, and these substituting groups connect by other key of ehter bond or some in the position of hydroxyl, or alternatively, and the position of hydroxyl can oxidized reaction or the reaction institute modification of some other types.
In addition, the part of hydroxyl of higly branched chain polyester polyol can be esterified.
The expression example of this class higly branched chain macromonomer comprises the structure for preparing by forming the higly branched chain fluidized polymer: by compound that contains at least one hydroxyl and the monocarboxylic acid reaction that contains at least two hydroxyls, carbon atom adjacent with carbonyl in monocarboxylic acid is a tertiary carbon atom, then, the hydroxyl end groups of polymkeric substance and unsaturated acid such as vinylformic acid, methacrylic acid-respons, or contain the acrylic compound reaction of isocyanate group.Also in " Angew.Chem.Int.Ed.Engl.29 " the 138th to 177 page (1990), disclose and comprised the example of ester bond as the multibranched polymer of repeated structural unit by people such as Tamalia.
The examples of compounds that contains at least one hydroxyl recited above comprises: a) aliphatic dihydroxy alcohol, alicyclic dibasic alcohol and aromatic diol, b) trivalent alcohol, c) tetravalent alcohol, d) sugar alcohol example, as sorbyl alcohol and N.F,USP MANNITOL, e) dehydration-nine-heptitols or Dipentaerythritol, f) alpha-alkyl glucosides methylglycoside for example, g) for example ethanol and hexanol of monohydric alcohol, h) molecular weight is no more than 8000 hydroxyl polymer-containing, it be by contain be selected from recited above a) to g) in the alkylene oxide or derivatives thereof reaction of one or more pure hydroxyls obtain.
The suitable aliphatic dibasic alcohol, the example of alicyclic dibasic alcohol and aromatic diol comprises 1,1, ammediol, 1,4-butyleneglycol, 1,5-pentanediol, 1,6-hexylene glycol, polytetrahydrofuran, dihydroxy methylpropane, neo-pentyl propane, 2-propyl group-2-ethyl-1, ammediol, 1, the 2-propylene glycol, 1,3 butylene glycol, glycol ether, triglycol, polyoxyethylene glycol, dipropylene glycol, tripropylene glycol and polypropylene glycol; Cyclohexanedimethanol and 1,3-diox-5,5-dimethanol; With 1,4-xylylene-glycol and 1-phenyl-1.
Suitable trivalent alcohol example comprises TriMethylolPropane(TMP), trimethylolethane, tri hydroxy methyl butane, glycerol, 1,2,5-hexanetriol.
Suitable tetravalent alcohol example comprises tetramethylolmethane, ditrimethylolpropane, Glycerol dimer and two trimethylolethane.
The aromatics example that contains at least two hydroxyls that are connected with aromatic ring comprises 1,3,5-trihydroxybenzene, 1,4-xylylene-glycol, 1-phenyl-1.
Comprise at least two hydroxyls, wherein adjacent with carboxyl carbon atom is that all substituted monocarboxylic example of the hydrogen atom of tertiary carbon atom comprises: dimethylol propionic acid, α, α-two (methylol) butyric acid, α, α, α-three (methylol) acetate, α, α-two (methylol) valeric acid, and α, α-two (methylol) propionic acid.By using such monocarboxylic acid, can suppress the decomposition reaction of ester, thereby form the higly branched chain polyester polyol.
The preferred catalyzer that uses in the preparation process of above-mentioned multibranched polymer, and suitable catalyzer example comprises: organo-tin compound is dialkyl stannic oxide for example, halogenated two alkane tin, the dialkyl tin dicarboxylate, or tin oxyethane (stannoxane), titanic acid ester is tetrabutyl titanate for example, and organic sulfonic acid, as Lewis acid and tosic acid.
Containing ehter bond is that the unitary higly branched chain macromonomer of repeating structure comprises by forming the structure that multibranched polymer prepares: by compound that contains at least one hydroxyl and the cyclic ether compounds reaction that contains at least one hydroxyl, then, the hydroxyl end groups of this polymkeric substance and unsaturated acid such as vinylformic acid, methacrylic acid or contain the acrylic compound reaction of isocyanate group, or with halogenation vinyl toluene such as the reaction of 4-1-chloro-4-methyl-benzene.In addition, it is synthetic that a kind of method for preparing multibranched polymer is based on Williamson (Williamson) ether, and comprise and make the compound that contains at least one hydroxyl and comprise two or more hydroxyls, and halogen atom ,-OSO
2OCH
3Or-OSO
2CH
3Compound send out should.
The compound that contains at least one hydroxyl can use top described same compound.
The suitable example that contains the cyclic ether compounds of at least one hydroxyl comprises 3-ethyl-3-(methylol)-trimethylene oxide (oxetane), 2,2,3-epoxy-1-butanols and 3,4-epoxy-1-butanols.
The compound that contains at least one hydroxyl in Williamson ether is synthetic can use a kind of in the compound recited above, is preferred although contain the aromatics of at least two hydroxyls that are connected with aromatic ring.The expression example of such compound comprises 1,3,5-trihydroxybenzene, 1, the inferior dimethylbenzene dimethanol of 4-and 1-phenyl-1.
In addition, comprise two or more hydroxyls, and halogen atom ,-OSO
2OCH
3Or-OSO
2CH
3Examples for compounds comprise: 5-(brooethyl)-1,3-dihydroxy-benzene, 2-ethyl-2-(brooethyl)-1, ammediol, 2-methyl-2-(brooethyl)-1, ammediol, and 2-(brooethyl)-2-(methylol)-1, ammediol.
The preferred catalyzer that uses in the process of the above-mentioned multibranched polymer of preparation, and suitable catalyzer example comprises BF
3Diethyl ether, FSO
3H, ClSO
3H, and HClO
4
In addition, contain amido linkage and be the unitary higly branched chain macromonomer of repeating structure and comprise that amido linkage wherein forms the structure of repeating unit by nitrogen-atoms, and the expression example of this structure be the product G eneration2.0 (PAMAM Dendrimer) by Dendriten Inc. production.
Along with being incorporated into the double key number order increase that the higly branched chain macromonomer props up chain end, also improve by the degree of branching with the styrene copolymerized higly branched chain polystyrene that obtains.The degree of branching of employed higly branched chain macromonomer (DB) can be by the definition of the formula (3) shown in following among the present invention, and excellent preferred branched degree (DB) value is 0.3 to 0.8:
DB=(D+L)/(D+T+L) (3) (wherein, D represents the unitary number of side chain, and L represents the number of linear unit, and T represents the number of terminal units)
D recited above, the value of T and L can by active methylene radical and according to
13The number of the second month in a season, uncle and quaternary carbon atom that C-NMR measures, or derived from this methylene radical reaction primary, the number decision of the second month in a season and tertiary N atom.For example the D value is corresponding to the number of quaternary carbon atom or the number of tertiary N atom, and the L value is corresponding to the number of tertiary carbon atom or the number of secondary nitrogen-atoms, and the T value is corresponding to the number of secondary carbon(atom) or the number of uncle's nitrogen-atoms.
For the weight-average molecular weight of restriction higly branched chain polystyrene for being no more than 10,000,000 value, the weight-average molecular weight of preferred higly branched chain macromonomer used in the present invention is 1000 to 15,000, more preferably 2000 to 5000.
By per 1 gram higly branched chain macromonomer, the quantity that is incorporated into the two keys that directly are connected with aromatic ring in the higly branched chain macromonomer is preferably 0.1 to 5.5 mmole, and more preferably 0.5 to 3.5 mmole per 1 restrains the higly branched chain macromonomer.If the quantity of two keys is lower than 0.1 mmole, be difficult to prepare the higly branched chain polystyrene of macromolecule, if instead the quantity of two keys greater than 5.5 mmoles, then the molecular weight of higly branched chain polystyrene increases excessively.
By higly branched chain macromonomer recited above and styrene polymerization, obtained composition of styrene resin of the present invention, it is included as the higly branched chain polystyrene of higly branched chain macromonomer and styrol copolymer and the mixture of the linear polystyrene that obtains simultaneously.
Known styrene polymerization reaction can be used for polyreaction.Though preferably adopt mass polymerization, suspension polymerization or solution polymerization are not particularly limited for polymerization system.Can under the condition of not using polymerization starter, carry out hot polymerization, but preferably use typical radical polymerization initiator.In addition, for example suspension agent or emulsifying agent can utilize the conventional material that is used for typical polystyrene production process to the auxiliary agent that needs of polymerization.
Based on higly branched chain macromonomer and cinnamic total amount, the ratio of preferred higly branched chain macromonomer is 50ppm to 1%, and more preferably 100 to 2000ppm.If the ratio of higly branched chain macromonomer is less than 50ppm, effect of the present invention just can fully not show.
Can add organic solvent in reaction system, to reduce the viscosity of reactant in the polyreaction, the example of suitable organic solvent comprises toluene, ethylbenzene, dimethylbenzene, acetonitrile, benzene, chlorobenzene, dichlorobenzene, methyl-phenoxide, cyanobenzene, dimethyl formamide, N,N-dimethylacetamide and methylethylketone.
Special under those big situations of higly branched chain macromonomer quantity, from suppressing the agglomerative angle, preferably with an organic solvent.Add organic solvent above-mentioned higly branched chain macromonomer quantity is significantly increased, and without any agglomerative danger.
Initiator to employed radical polymerization has no particular limits, and conventional material suits, and it comprises that the ketone peroxide acetal is as 1,1-two (t-butyl peroxy) hexanaphthene, 2,2-two (t-butyl peroxy) butane and 2,2-two (4,4-di-t-butyl peroxide cyclohexyl) propane; Hydroperoxide such as cumene hydroperoxide, t-butyl hydroperoxide; Dialkyl such as di-t-butyl peroxide, dicumyl peroxide and peroxidation two uncle's hexyls; Peroxidation two acyls such as peroxidation benzene (first) acyl, peroxidation two cinnyls; Peroxyester such as peroxidation phenylformic acid tertiary butyl ester, peroxidation m-phthalic acid di-t-butyl ester and peroxidation sec.-propyl-butyl carbonate; And N, N '-Diisopropyl azodicarboxylate, N, N '-azo (hexanaphthene-1-nitrile), N, N '-azo (2-methylbutyronitrile), N, N '-azo (2, the 4-methyl pentane nitrile) and N, N '-azo [2-(methylol) propionitrile].These polymerization starters can use separately, but also two or more compounds are used in combination.
In addition, can also add chain-transfer agent, can be not too high with the molecular weight of guaranteeing composition of styrene resin.Chain-transfer agent can use the simple function group chain-transfer agent that only contains a chain transfer group, also can use the polyfunctional group chain-transfer agent that contains a plurality of chain transfer groups.Suitable simple function group chain-transfer agent example comprises alkyl sulfhydryl and mercaptoacetate.
Suitable polyfunctional group chain-transfer agent example comprises by hydroxyl groups and Thiovanic acid or 3-thiohydracrylic acid and carries out esterification and the compound that obtains, wherein polyvalent alcohol for example 1, the 2-ethylidene glycol, neopentyl glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tripentaerythritol or sorbyl alcohol.
Prepare the method for composition of styrene resin of the present invention by higly branched chain macromonomer and cinnamic one-step polymerization except that recited above, can also be by respectively synthesizing linear polystyrene and higly branched chain polystyrene, then both are mixed and prepare the composition of styrene resin of suitable proportion between higly branched chain polystyrene and the linear polystyrene.
In composition of styrene resin of the present invention, because higly branched chain polystyrene and linear polystyrene evenly disperse (interdispersed) mutually and mix on molecular level, and intertwine, in the folded test of folding etc., composition of styrene resin shows the folding strength better than conventional linear styrene.On molecular level, evenly disperse mutually and be dispersed in aspect together the resin combination obtaining wherein higly branched chain polystyrene and linear polystyrene, higly branched chain macromonomer and the reaction of cinnamic one-step polymerization are preferred, and it is better than wherein preparing respectively the method that higly branched chain polystyrene and linear polystyrene mix then.Consider that from the production efficiency aspect one-step polymerization reaction also is preferred.
When adopting gel permeation chromatography to measure the molecular weight of polystyrene resin composite of the present invention, peak from linear polystyrene appears at the lower molecular weight side, and the peak from the higly branched chain polystyrene appears at the high molecular side, and can be with the area below two peaks than being used for determining two types the proportion of composing of polystyrene and the weight-average molecular weight of each polystyrene.
Be the moulding product of guaranteeing that this has following performance by the polystyrene resin composite preparation of invention: good melt tension, good intensity is folding strength for example, and show high melt mass flow rate and good forming ability, the weight-average molecular weight of polystyrene resin composite neutral line polystyrene typically is 200,000 to 350,000, the weight-average molecular weight of higly branched chain polystyrene typically is 1,000,000 to 10,000,000, more preferably 2,000,000 to 5,000,000.If the weight-average molecular weight of higly branched chain polystyrene is lower than 1,000,000, can not reach satisfied intensity so, if instead molecular weight surpasses 10,000,000, can not reach the forming ability of satisfactory level.
In addition, the weight-average molecular weight of polystyrene resin composite typically is 250,000 to 700,000, and more preferably 280,000 to 500,000.In addition, the weight ratio between preferred polystyrene resin composite neutral line polystyrene and the higly branched chain polystyrene is a linear polystyrene: the polystyrene of higly branched chain is 99.1: 0.9 to 75: 25, and more preferably 99.1: 0.9 to 81: 15.
Polystyrene resin composite of the present invention is included in the higly branched chain polystyrene that conventional linear polystyrene does not have the ultra-high molecular weight of discovery, although but polystyrene resin composite of the present invention comprises the component of such ultra-high molecular weight, but gelatin phenomenon does not obviously exist, and causes composition to be soluble in the organic solvent.
The melt mass flow rate of polystyrene resin composite of the present invention is satisfied with the relation with weight-average molecular weight in formula (1) expression, and has the conventional linear polystyrene higher melt mass flow rate more identical than weight-average molecular weight:
Formula (1)
MFR (g/10min) 〉=45 * exp (0.1 * Mw * 10
-4) (wherein, MFR and Mw represent composition of styrene resin melt mass flow rate and weight-average molecular weight respectively)
Melt mass flow rate (MFR g/10min) is meant the method according to JIS K7210:99, at 200 ℃, and the value of under the load of 49N, measuring.
If the MFR value of polystyrene resin composite is lower than the value of being calculated by following formula (1), then can not obtain the forming ability of good level.
In addition, melt tension, it be satisfied with the relation with weight-average molecular weight in formula (2) expression, and the melt tension of the conventional linear polystyrene more identical than weight-average molecular weight is higher as the index of expression polystyrene resin composite intensity of the present invention and forming ability:
Formula (2)
MT(g)≥0.07Mw×10
-4+1.8
(wherein MT and Mw are expressed as the melt tension and the weight-average molecular weight of styrene resin synthetics respectively)
Tension force when melt tension (MT) is described the resin fusing, and as the index of representing resin rigidity and forming ability.Tension force during the resin fusing increases along with the increase of melt tension, thereby the production rate of extrusion molding is increased.
The melt tension of being reported (MT) value is by using Capirograph (1B type in the present invention, by Toyo Seisaku-sho, Ltd. make) measure, and be meant MT (g) value of measuring under the following conditions: length capillaceous (L) 50.80mm and diameter (D) 1.27mm, diameter (B) is 60m/s for bucket and the velocity of shear of 9.55mm, can make sample produce under the temperature of melt viscosity of 1300Pas and the speed of removing (taking-off speed) of one 20m/min.If the MT of styrene resin is lower than the value that calculates by in the formula (2), the rigidity of resin combination and forming ability will aggravate so.
The composition of styrene resin that the present invention comprises the higly branched chain polystyrene is a high-molecular weight, compare with conventional linear polystyrene with similar molecular weight, it shows higher melt mass flow rate, good flowability in composition of styrene resin preparation and the moulding process, the throughput of good level and processing characteristics.The result, composition of styrene resin of the present invention can be used for than the more wide various Application Areas of conventional composition, can be used for by various forming methods injection moulding for example, extrinsion pressing, vacuum forming, the air-pressure forming method, the crushed foam method of forming, calendering and blow molding method prepare in the moulding product.
Embodiment
Embodiment
It below is the more detailed description that the present invention is based on a series of embodiment.The present invention is in no way limited to the embodiment of following appearance.It at first is the description of the measuring method that adopted.
(gpc measurement method)
Use high-speed liquid chromatography (HLC-8220GPC; make by Tosoh company); the RI detector is equipped with; use tsk gel G6000H * 1+G5000H * 1+G4000H * 1+G3000H * 1+TSK guard column (guard column) H * 1-H; the THF solvent; 1.0ml/min velocity of flow, 40 ℃ temperature.
Use multistation GPC-8020 to carry out stratographic analysis, with analysis software two peaks of appearance are separated, and can measure the weight-average molecular weight of linear polystyrene and higly branched chain polystyrene, the results are shown in table 1 to table 3.Mark P 1Mw in the table and P2Mw refer to the weight-average molecular weight of linear polystyrene and higly branched chain polystyrene respectively.In addition, the weight-average molecular weight of the whole resin combination that obtains before two peak compartment analysises is recorded as total molecular weight, and the maximum value of the Mw that records is recorded as maximum Mw.
The chromatogram of embodiment 2 is shown among Fig. 2.Transverse axis is represented the residence time, and the longitudinal axis represents peak intensity, and represents higher molecular weight in the component peaks in short residence time(SRT) district more.Among the figure, solid line is represented the peak that actual measurement obtains, and dotted line represents the peak that produces as analytical results, and higly branched chain polystyrene (P2) is represented at the peak of stratographic higher molecular weight side, and linear polystyrene (P1) is represented at the peak of lower molecular weight side.
(NMR measuring method)
With nucleus magnetic resonance (
1H-NMR) be used for measuring the quantity of the two keys of vinyl in the higly branched chain macromonomer (ethyleny), and be recorded as the mole number of the sample of every weight unit.Will
13C-NMR be used for measuring active methylene radical and by the reaction of this methylene radical the number of deutero-second month in a season, uncle and quaternary carbon atom, measure the degree of branching of higly branched chain macromonomer thus.
(measuring method of melt mass flow rate)
Measure according to JIS K7210:99.Measuring condition comprises 200 ℃ temperature, the load of 49N.(measuring method of melt tension)
Use Capirograph (1B type, by Toyo Seisaku-sho, Ltd. makes) to measure melt tension.The length capillaceous (L) of employed device is that 50.80mm and diameter (D) are 1.27mm, and measure under MT (g) the value condition below: diameter (B) is 60m/s for bucket and the velocity of shear of 9.55mm, can make sample produce under the temperature of melt viscosity of 1300Pas and the speed of removing of one 20m/min.
(measuring method of second-order transition temperature)
Prepare the film that thickness is 0.4mm by specimen material, and be to use dynamic viscoelastic instrument (DMA is made by Ltd) to measure second-order transition temperature (Tg).
(being insoluble to the measuring method of toluene part)
In toluene, its concentration is 1g/100ml with sample dissolution, and passes through 12 the insoluble part that 000rpm came in the separation solution in centrifugal 30 minutes.With centrifugal go out to be insoluble to the toluene part dry, measure exsiccant weight, and use following formula to determine to be insoluble to the toluene part:
Be insoluble to toluene part (%)=[exsiccant is insoluble to the weight/example weight of toluene part] * 100
(measuring method of folding strength)
With biaxial stretch-formed machine of while, the profiled sheeting that will be prepared by hot pressing changes the thin slice of thickness 0.2mm into.Draft temperature is 130 ℃, will all be set to 2.3 times at the draw ratio of both direction.By following method, the part of this thin slice is used for measuring folding strength: according to JIS P-8115, needed folding multiplicity when measuring thin slice and fractureing.
Synthetic (M-m1) of (reference example 1) higly branched chain macromonomer
1000 milliliters the separating in the flask of whipping appts, dropping funnel, thermometer, logical nitrogen equipment and bubbler be equipped with, under nitrogen atmosphere, 4-bromine two (vinyloxy group) phenylacetonitriles of 35 grams are dissolved in 800 milliliters the methyl-sulphoxide (DMSO).Flask is placed water-bath, and when internal temperature reaches 30 ℃, drip 66 milliliter 50% aqueous sodium hydroxide solution.The mixture that obtains was stirred 2 hours, and wherein temperature remains in 30 ℃, obtains the precursor of higly branched chain macromonomer.Restrain the 4-1-chloro-4-methyl-benzenes by Dropwise 5 in reaction mixture 6.6 subsequently, and then continue to stir 2 hours, formed the solution of higly branched chain macromonomer.
Filtering product solution is removed solid part, and the filtrate that obtains is poured in 5 liters of methyl alcohol that contain 225 milliliter of 5 mol hydrochloric acid soln, thereby is settled out the higly branched chain macromonomer.The higly branched chain macromonomer that filtering-depositing goes out under suction, and use distilled water and methanol wash at every turn, wash altogether 3 times.With gained higly branched chain macromonomer drying under reduced pressure 24 hours, obtain 24 gram higly branched chain macromonomers (M-m1).
Obtain higly branched chain macromonomer (M-m1) thus with gpc measurement, show that its weight-average molecular weight is 11,000.In addition,
1The quantity that H-NMR measures the two keys that directly are connected with aromatic ring that confirm introducing is 2.66 mmole/grams.Degree of branching value is 0.6.
Synthesizing of (reference example 2) higly branched chain macromonomer (M-m2)
Except that 4-bromine two (vinyloxy group) phenylacetonitrile that replaces with 4-tosyloxy two (vinyloxy group) phenylacetonitrile in the reference example 1, synthesize with the method identical, and be able to the higly branched chain macromonomers (M-m2) of 25 grams with reference example 1.The weight-average molecular weight of product higly branched chain macromonomer (M-m2) is 5,800.
1It is 2.04 mmole/grams that H-NMR measures the quantity that shows the two keys of introducing that directly are connected with aromatic ring.
Synthesizing of (reference example 3) higly branched chain macromonomer (M-m3)
Except that 66 milliliter 50% the aqueous sodium hydroxide solution that replaces with 6.6 milliliter 50% aqueous sodium hydroxide solution in the reference example 2, synthesize with the method identical, and obtain the higly branched chain macromonomers (M-m3) of 29 grams with reference example 1.The weight-average molecular weight of product higly branched chain macromonomer (M-m3) is 7,000.
1It is 1.84 mmole/grams that H-NMR measures the quantity that shows the two keys of introducing that directly are connected with aromatic ring.
Synthesizing of (reference example 4) higly branched chain macromonomer (M-m4)
(synthesizing of higly branched chain polyether polyol 1)
At ambient temperature, be equipped with 2 liters of flasks of agitator, thermometer, dropping funnel and condenser, 50.5 gram ethoxylation tetramethylolmethanes (5 moles of ethylene oxide affixtures of tetramethylolmethane) and 1 gram BF pack into
3Diethyl ether solution (50%), and with mixture heating up to 110 ℃, in 35 minutes, slowly add 3-ethyl-3-(methylol) trimethylene oxide of 450 grams then, the liberated heat of control reaction simultaneously.Step back when the heat of reaction looses, again in 120 ℃ with reaction mixture heated and stirred 3.5 hours, cool to room temperature then.
The weight-average molecular weight of product higly branched chain polyether polyol is 3,500, and hydroxyl value is 510.(higly branched chain polyethers 1 synthetic that contains methacryloyl and ethanoyl)
50 gram higly branched chain polyether polyols of preparation in (higly branched chain polyether polyol 1 synthetic) above the reaction vessel that be equipped with agitator, thermometer, contains the Dean-Rodney Stark decantor of condenser and gas introduction tube is packed into, 13.8 gram methacrylic acid, 150 gram toluene, 0.06 the p-methyl benzenesulfonic acid of gram quinhydrones and 1 gram, and under non-pressurized condition, stir the mixture and heat, feed the nitrogen that contains 7% oxygen to mixing solutions with the speed of 3 ml/min simultaneously.Regulate degree of heat, make the distillment amount that enters decantor for per hour 30 restraining.Continue heating and reach 2.9 grams up to dehydrating amount.
After reaction was finished, cooling mixture added 36 gram diacetyl oxides and 5.7 gram thionamic acids, and stirred the mixture that obtains down 10 hours in 60 ℃.Subsequently, with 50 grams, 5% aqueous sodium hydroxide solution product purging compound 4 times, to remove any residual acetate and quinhydrones, with the aqueous sulfuric acid washing of 50 grams 1% 1 time, 50 restrain the water product washs 2 times then.Add 0.02 gram p methoxy phenol (methoquinone) in the organic phase that obtains thus, under reduced pressure remove then and desolvate, 7% oxygen obtains the higly branched chain polyethers that 60 grams contain pseudoallyl and ethanoyl thus by system simultaneously.The weight-average molecular weight of the higly branched chain polyethers that obtains thus is 4500, and pseudoallyl and the conjugation of ethanoyl in the higly branched chain polyether polyol are respectively 35% and 60%.
Synthesizing of (reference example 5) higly branched chain macromonomer compound (M-m5)
(higly branched chain polyethers 1 synthetic that contains styryl and ethanoyl)
50 gram higly branched chain polyether polyols of preparation in (higly branched chain polyether polyol 1 synthetic) above the reaction vessel that be equipped with agitator, contains condenser, dropping funnel and the thermometer of drying tube is packed into, 100 gram tetrahydrofuran (THF)s and 4.3 gram sodium hydrides, and at room temperature stir the mixture, in 1 hour time limit, drip 26.7 gram 4-1-chloro-4-methyl-benzenes to reaction system, and in 50 ℃ with the reaction mixture restir that obtains 4 hours.
After reaction was finished, cooling mixture added 34 gram diacetyl oxides and 5.4 gram thionamic acids, and the mixture that obtains was stirred 10 hours in 60 ℃.Subsequently, remove tetrahydrofuran (THF) under the decompression, the mixture that obtains is dissolved in the 150 gram toluene, and the aqueous sodium hydroxide solution sample with 50 grams 5% washs toluene solution 4 times, to remove any residual acetate, the aqueous sulfuric acid with 50 grams 1% washs 1 time then, 50 gram water samples washings 2 times.Decompression removes from organic phase and desolvates down, obtains the higly branched chain polyethers that 70 grams contain styryl and ethanoyl.The weight-average molecular weight of the higly branched chain polyethers that obtains thus is 5300.Styryl and the ethanoyl conjugation in the higly branched chain polyether polyol is respectively 40% and 55%.
Synthesizing of (reference example 6) higly branched chain macromonomer (M-m6)
(the synthetic PAMAM Dendrimer that contains styryl)
The reaction vessel that be equipped with agitator, contains condenser, dropping funnel and the thermometer of drying tube 50 gram PAMAM dendrimer (the ProductName Generation 2.0 that pack into, by Dendritech Inc. preparation) methanol solution (20 weight %), and do not stop to stir, under reduced pressure remove methyl alcohol.Subsequently, add 50 gram tetrahydrofuran (THF)s and 2.6 gram potassium hydroxide fine powders, and stir the mixture that obtains under the room temperature, in reaction system, drip 7.2 gram 4-1-chloro-4-methyl-benzenes in 10 minutes, then with reaction mixture in 50 ℃ of restir 4 hours.
After reaction was finished, cooling mixture then by the solids removed by filtration material, was removed tetrahydrofuran (THF) in decompression, obtained the PAMAM dendrimer that 14 grams comprise styryl.The styryl content of Dendrimer product is 3.0 mmole/grams.
Synthesizing of (reference example 7) higly branched chain macromonomer (M-m7)
(higly branched chain polyether polyol 2 synthetic that contains styryl and ethanoyl)
Under nitrogen gas stream, can nitrogen-sealed and be equipped with the reaction vessel of the dropping funnel of agitator, condenser, light shield and thermometer 0.5 gram anhydrous 1 of packing into, 3, the 5-trihydroxybenzene, 29 gram salt of wormwood, 2.7 gram hexaoxacyclooctadecane-6-6 and 180 gram acetone, and under situation about ceaselessly stirring the mixture, drip in 3 hours and comprise 21.7 gram 5-(brooethyl)-1, the solution of 3-dihydroxy-benzene and 180 gram acetone.Reflux is mixed just thing under stirring continuously, and up to 5-(brooethyl)-1, the 3-dihydroxy-benzene disappears.
Subsequently, add 10.3 gram 4-1-chloro-4-methyl-benzenes, under ceaselessly stirring, continue reflux, disappear up to the 4-1-chloro-4-methyl-benzene.Add 4 gram diacetyl oxides and 0.6 gram thionamic acid to reaction mixture then, stir under the room temperature and spend the night.With postcooling, remove by filter the solid matter in the reaction mixture, decompression removes down and desolvates.The mixture that obtains is dissolved in the methylene dichloride, and washes with water three times, then dichloromethane solution is added dropwise in the hexane, so that higly branched chain polyethers precipitation.Filter and dry sediment, obtain the higly branched chain polyether polyol that 14 grams contain styryl and ethanoyl.Weight-average molecular weight is 4050, and the content of styryl is 3.3 mmole/grams.
Synthesizing of (reference example 8) higly branched chain macromonomer thing (M-m8)
(the synthetic higly branched chain polyether polyol that contains methacryloyl and ethanoyl synthetic)
7% airway is equipped with, thermometer, the reaction vessel that contains the Dean-Rodney Stark decantor of condenser and agitator 10 grams " Boltom H20 " of packing into, 1.25 grams, two fourth stannic oxide, 100 grams contain pseudoallyl and restrain quinhydrones as the methyl methacrylate (B) and 0.05 of functional group.The reaction mixture that heating under agitation obtains is simultaneously to the oxygen of mixture with the speed feeding 7% of 3 ml/min.Regulate degree of heat, make the distillment amount that flows into decantor for per hour 15 to 20g, and reaction continues 6 hours, during this period, per hour shifts distillment once from decantor, and the methyl methacrylate of adding equivalent.
After reaction is finished, remove methyl methacrylate under the decompression, and add 10g diacetyl oxide and 2g thionamic acid, stirred 10 hours under the room temperature, make any remaining hydroxyl closure (cap).Remove by filter thionamic acid then, remove diacetyl oxide and acetate under the decompression subsequently, residuum is dissolved in the 70g ethyl acetate, aqueous sodium hydroxide solution sample with 20g 5% washes 4 times, to remove remaining quinhydrones, aqueous sulfuric acid sample with 20 grams 7% washs 2 times then, 20 gram water samples washings 2 times.Add 0.0045 gram p methoxy phenol to the organic phase that obtains thus, under reduced pressure remove then and desolvate, 7% oxygen obtains the higly branched chain polyethers that 12 grams contain pseudoallyl and ethanoyl thus by system simultaneously.The weight-average molecular weight of the higly branched chain polyethers that obtains thus is 2860, and number-average molecular weight is 3770, and pseudoallyl and the conjugation of ethanoyl in higly branched chain polyether polyol (A) are respectively 55% and 40%.
(embodiment 1)
5 liters of stainless steel reaction containers that are equipped with turbine blade, the 2000 milliliters of ion exchanged waters of packing into, then add and dissolve 10 and restrain partly-hydrolysed polyvinyl alcohol and 0.05 Sodium dodecylbenzene sulfonate that restrains as suspension stabilizer, the 1000g vinylbenzene that adds the higly branched chain macromonomer (M-m1) that comprises the 0.6g uniform dissolution successively, the peroxidized t-butyl perbenzoate of 2.8g benzoyl peroxide and 0.6g.
Subsequently, with the air in the nitrogen replacement reaction vessel, stirred reaction mixture under 500rpm, elevated temperature carries out suspension polymerization 6 hours, and then carried out under 117 ℃ 3 hours under 92 ℃ simultaneously.With the particulate state polystyrene resin washing that generates, dehydration and dry obtains the 980g composition of styrene resin.Use cylinder temperature is 230 ℃ a forcing machine, with this resin granulation.The composition of styrene resin that obtains is used for preparing as at the thin slice described in the folding strength measuring method, and measures folding strength.The result of folding strength is 12 times repetition.
(embodiment 2)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m2), prepare composition of styrene resin with the method identical with embodiment 1.The composition of styrene resin that obtains is used for preparing as at the thin slice described in the folding strength measuring method, and measures folding strength.The result of folding strength is 13 times repetition.
(embodiment 3)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m3), prepare composition of styrene resin with the method identical with embodiment 1.
(embodiment 4)
The amount of the higly branched chain macromonomer (M-m1) in will adding embodiment 1 is changed into the 0.2g by 0.6g, prepares composition of styrene resin with the method identical with embodiment 1.
(embodiment 5)
The amount of the higly branched chain macromonomer (M-m1) in will adding embodiment 1 is changed into the 0.4g by 0.6g, prepares composition of styrene resin with the method identical with embodiment 1.
(embodiment 6)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m4), prepare composition of styrene resin with the method identical with embodiment 1.
(embodiment 7)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m5), prepare composition of styrene resin with the method identical with embodiment 1.
(embodiment 8)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m6), prepare composition of styrene resin with the method identical with embodiment 1.
(embodiment 9)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m7), prepare composition of styrene resin with the method identical with embodiment 1.
(embodiment 10)
Except that the higly branched chain macromonomer (M-m1) among the embodiment 1 is changed into the higly branched chain macromonomer (M-m8), prepare composition of styrene resin with the method identical with embodiment 1.
(comparative example 1)
Except that not adding macromonomer (M-m1), prepare composition of styrene resin with the method identical with embodiment 1.The composition of styrene resin that obtains is used for preparing as at the thin slice described in the folding strength measuring method, and measures folding strength.The result of folding strength is 7 times repetition.
(comparative example 2)
Except that the reaction times changes 7 hours into, and with 1 of 3.6g, 1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane and 0.3g peroxidized t-butyl perbenzoate replace outside 2.8g benzoyl peroxide and the 0.6g peroxidized t-butyl perbenzoate, and the method identical with comparative example 1 is used for preparing linear polystyrene.
(comparative example 3)
Remove with 1 of 2.3g, 1-two (t-butyl peroxy)-3,3,5-trimethyl-cyclohexane and 0.5g peroxidized t-butyl perbenzoate replace outside 2.8g benzoyl peroxide and the 0.6g peroxidized t-butyl perbenzoate, and the method identical with comparative example 1 is used for preparing linear polystyrene.
(comparative example 4)
Remove to add outside whiteruss (Daphne Oil CP-50S, by Idemitsu Kosan.Co., Ltd. preparation) and the vinylbenzene, the method identical with comparative example 3 is used for preparing linear polystyrene.
(embodiment 11)
Except that the add-on with higly branched chain macromonomer (M-m1) changes into the 1.5g, to prepare composition of styrene resin with the identical method of embodiment 1.
(embodiment 12)
The linear polystyrene of the composition of styrene resin of embodiment 6 preparation and comparative example 2 preparations is carried out melt kneading by 7: 3 weight ratio blended mixture in forcing machine, obtain a kind of composition of styrene resin of new composition change thus.
Table 1
| | | | Embodiment 4 | |
| Macromonomer | M-m1 | M-m2 | M-m3 | M-m1 |
| The add-on of macromonomer (ppm) | 600 | 600 | 600 | 200 |
| Total molecular weight (* 10 -4) | 38.9 | 42.5 | 45.8 | 32.1 |
| P1Mw(×10 -4) | 31.8 | 33.0 | 38.6 | 32.9 |
| P2Mw(×10 -4) | 221 | 224 | 262 | 213 |
| P1/P2(-) | 93/7 | 93/7 | 94/6 | 99/1 |
| Maximum Mw (* 10 -4) | 1,767 | 1,326 | 3,019 | 663 |
| MFR(g/10min) | 1.3 | 0.9 | 0.5 | 2.7 |
| MT(g) | 5.2 | 5.7 | 6.5 | 4.6 |
| Be insoluble to the part (weight %) of | 0 | 0 | 0 | 0 |
| Tg(℃) | 106 | 106 | 106 | 106 |
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Macromonomer | - | - | - | - |
| The add-on of macromonomer (ppm) | - | - | - | - |
| Total molecular weight (* 10 -4) | 25.5 | 33.0 | 40.2 | 40.2 |
| P1Mw(×10 -4) | 25.5 | 33.0 | 40.2 | 40.2 |
| P2Mw(×10 -4) | - | - | - | - |
| P1/P2(-) | 100/0 | 100/0 | 100/0 | 100/0 |
| Maximum Mw (* 10 -4) | 490 | 500 | 500 | 500 |
| MFR(g/10min) | 2.2 | 1.4 | 0.6 | 0.9 |
| MT(g) | 3.5 | 4.0 | 4.4 | 4.2 |
| Be insoluble to the part (weight %) of | 0 | 0 | 0 | 0 |
| Tg(℃) | 105 | 106 | 106 | 98 |
Table 3
| Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Macromonomer | M-m1 | M-m4 | M-m5 | M-m6 |
| The add-on of macromonomer (ppm) | 400 | 600 | 600 | 600 |
| Total molecular weight (* 10 -4) | 37.3 | 44.5 | 42.7 | 40.1 |
| P1Mw(×10 -4) | 33.2 | 33.0 | 31.9 | 32.5 |
| P2Mw(×10 -4) | 216 | 274 | 225 | 223 |
| P1/P2(-) | 96/4 | 93/7 | 95/5 | 96/4 |
| Maximum Mw (* 10 -4) | 935 | 2,632 | 2,584 | 2,088 |
| MFR(g/10min) | 1.5 | 0.9 | 1.1 | 1.2 |
| MT(g) | 4.8 | 5.9 | 5.1 | 5.0 |
| Be insoluble to the part (weight %) of | 0 | 0 | 0 | 0 |
| Tg(℃) | 106 | 106 | 106 | 106 |
Table 4
| Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Macromonomer | M-m7 | M-m8 | M-m1 | M-m1 |
| The add-on of macromonomer (ppm) | 600 | 600 | 1,500 | 1,050 |
| Total molecular weight (* 10 -4) | 46.3 | 45.4 | 55.3 | 48.2 |
| P1Mw(×10 -4) | 32.6 | 36.0 | 44.8 | 42.2 |
| P2Mw(×10 -4) | 278 | 262 | 246 | 242 |
| P1/P2(-) | 93/7 | 93/7 | 90/10 | 93/7 |
| Maximum Mw (* 10 -4) | 2,993 | 3,326 | 2,761 | 2,761 |
| MFR(g/10min) | 0.6 | 0.7 | 0.5 | 0.6 |
| MT(g) | 6.7 | 7.5 | 9.5 | 8.7 |
| Be insoluble to the part (weight %) of | 0 | 0 | 0 | 0 |
| Tg(℃) | 106 | 106 | 106 | 106 |
The weight-average molecular weight of embodiment 1 to 10 and comparative example 1 to 3 and MFR value relation are shown among Fig. 3.Transverse axis is represented molecular weight Mw (* 10
-4), the longitudinal axis is represented MFR value (g/10min), and in the drawings, small circle is represented the result of embodiment composition of styrene resin, square is represented the result of comparative example linear polystyrene.Obviously, it is big that the polyethylene resin composition of the present invention that comprises the higly branched chain polystyrene has high weight-average molecular weight, also shows high relatively MFR value simultaneously.
From table 1,2 and 3 be significantly, the polyethylene resin composition of the present invention conventional linear polystyrene more identical than weight-average molecular weight that comprises the higly branched chain polystyrene has higher melt mass flow rate, melt tension and folding strength value, thereby provide forming ability, rigidity and the intensity of good level.
Claims (11)
1. composition of styrene resin, it comprises that a kind of weight-average molecular weight is 200,000 to 350,000 linear polystyrene and a kind of be 1,000 by higly branched chain macromonomer and styrene copolymerized that obtain, weight-average molecular weight, 000 to 10,000,000 higly branched chain polystyrene, it has 250,000 to 700,000 weight-average molecular weight and satisfy the melt mass flow rate (MFR) and the melt tension (MT) of following formula (1) and (2) respectively:
MFR(g/10min)≥45×exp(-0.1×Mw×10
-4) (1)
Wherein, MFR and Mw represent the melt mass flow rate and the weight-average molecular weight of composition of styrene resin respectively, and described melt mass flow rate is according to JIS K7210:99 method, at 200 ℃, and the value of under the load of 49N, measuring,
MT(g)≥0.07Mw×10
-4+1.8 (2)
Wherein, MT and Mw represent the melt tension and the weight-average molecular weight of composition of styrene resin respectively.
2. the polystyrene resin composite of claim 1, wherein said higly branched chain polystyrene comprises the branched structure that contains electron withdrawing group and tertiary carbon atom, in described tertiary carbon atom, three keys except that a key that is connected with electron withdrawing group all are connected with other carbon atom.
3. the composition of styrene resin of claim 2 wherein restrains described higly branched chain polystyrene by per 1, and the quantity of the electron withdrawing group in the branched structure is 2.5 * 10
-4To 5.0 * 10
-1Mmole.
4. the composition of styrene resin of claim 1, wherein said higly branched chain polystyrene is a kind of (A) higly branched chain macromonomer and (B) cinnamic multipolymer, described higly branched chain macromonomer (A) comprises branched structure that contains electron withdrawing group and tertiary carbon atom and the two keys that directly are connected with aromatic ring, in described tertiary carbon atom, three keys except that a key that is connected with electron withdrawing group all are connected with other carbon atom.
5. the composition of styrene resin of claim 4 wherein restrains described higly branched chain macromonomer by per 1, and the degree of branching of higly branched chain macromonomer is 0.3 to 0.8, and the quantity of the described two keys that directly are connected with aromatic ring is 0.1 to 5.5 mmole.
6. the composition of styrene resin of claim 4, wherein the higly branched chain macromonomer has and comprises
Side chain by the repeating unit of the expression of the general formula (I) shown in following:
General formula (I)
Wherein, Y
1Expression is selected from-CN-NO
2,-CONH
2,-CON (R)
2,-SO
2CH
3And-P (=O) (OR)
2In electron withdrawing group, wherein R represents alkyl or aryl, Y
2The expression arylidene ,-O-CO-or-NH-CO-, and Z represents to be selected from-(CH
2)
nO-,-(CH
2CH
2O)
n-,-(CH
2CH
2CH
2O)
n-in group, if Y
2For-O-CO-or-NH-CO-, then Z represents-(CH
2)
n-,-(CH
2)
nAr-,-(CH
2)
nO-Ar-,-(CH
2CH
2O)
n-Ar-, or-(CH
2CH
2CH
2O)
n-Ar-, wherein Ar represents arylidene, and n represents the integer of 1-12.
7. method for preparing the composition of styrene resin of claim 1, it is characterized in that, (A) the higly branched chain macromonomer carries out radical polymerization with (B) vinylbenzene, described higly branched chain macromonomer (A) comprises branched structure that contains electron withdrawing group and tertiary carbon atom and the two keys that directly are connected with aromatic ring, in described tertiary carbon atom, three keys except that a key that is connected with electron withdrawing group all are connected with other carbon atom.
8. the composition of styrene resin of claim 1, wherein said higly branched chain polystyrene comprise to contain and are selected from ester bond, the branched structure of the repeated structural unit in ehter bond and the amido linkage.
9. the composition of styrene resin of claim 8, it is (A) higly branched chain macromonomer and (B) cinnamic multipolymer, described higly branched chain macromonomer comprises to contain and is selected from ester bond, the branched structure of the repeated structural unit in ehter bond and the amido linkage and at the two keys of a terminated.
10. the composition of styrene resin of claim 9, by the described higly branched chain macromonomer of per 1 gram, the degree of branching of higly branched chain macromonomer is 0.3 to 0.8, and described quantity at the two keys of a terminated is 0.1 to 5.5 mmole.
11. method for preparing the composition of styrene resin of claim 8, it is characterized in that, (A) the higly branched chain macromonomer carries out radical polymerization with (B) vinylbenzene, described higly branched chain macromonomer comprises to contain and is selected from ester bond, the branched structure of the repeated structural unit in ehter bond and the amido linkage and at the two keys of a terminated.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23625/2002 | 2002-01-31 | ||
| JP2002023625 | 2002-01-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1625581A CN1625581A (en) | 2005-06-08 |
| CN1276936C true CN1276936C (en) | 2006-09-27 |
Family
ID=27654459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038029499A Expired - Lifetime CN1276936C (en) | 2002-01-31 | 2003-01-30 | Styrene resin composition and process for producing the same |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US7049369B2 (en) |
| EP (1) | EP1471111B1 (en) |
| KR (1) | KR100848345B1 (en) |
| CN (1) | CN1276936C (en) |
| CA (1) | CA2474454C (en) |
| DE (1) | DE60335344D1 (en) |
| TW (1) | TWI278483B (en) |
| WO (1) | WO2003064524A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8787615B2 (en) | 2003-06-13 | 2014-07-22 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding watermarks |
| US8972033B2 (en) | 2006-10-11 | 2015-03-03 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding codes in compressed audio data streams |
| US9191581B2 (en) | 2004-07-02 | 2015-11-17 | The Nielsen Company (Us), Llc | Methods and apparatus for mixing compressed digital bit streams |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE502005002521D1 (en) * | 2004-08-10 | 2008-02-21 | Basf Ag | POLYMER BLENDS OF STYROLCOPOLYMERS AND HYPER-BRANCHED POLYCARBONATES OR POLYESTERS |
| DE102006058202A1 (en) * | 2006-12-11 | 2008-06-12 | Merck Patent Gmbh | Process for the preparation of dispersions |
| JP4345035B2 (en) * | 2007-09-11 | 2009-10-14 | Ｄｉｃ株式会社 | Resin composition for light diffusion plate, light diffusion plate and method for producing the same |
| JP4758497B2 (en) * | 2008-07-10 | 2011-08-31 | 株式会社リコー | Cleaning device and cleaning method |
| US8242212B2 (en) | 2010-03-31 | 2012-08-14 | Fina Technology, Inc. | Polystyrene blends |
| US9096698B2 (en) | 2012-08-09 | 2015-08-04 | Americas Styrenics, LLC | Styrenic resin incorporating recycled polystyrene |
| US11603422B2 (en) * | 2019-12-30 | 2023-03-14 | Rohm And Haas Electronic Materials Llc | Polymeric resin for dielectric applications |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4585825A (en) * | 1983-09-30 | 1986-04-29 | The Dow Chemical Company | Monovinylidene aromatic polymer resins having added amounts of high molecular weight polymer |
| DE68915658T2 (en) * | 1988-09-09 | 1994-09-15 | Nippon Catalytic Chem Ind | Optical material containing a high refractive index resin. |
| JPH03160007A (en) * | 1989-11-20 | 1991-07-10 | Tokuyama Soda Co Ltd | Copolymer and its production |
| US5132384A (en) * | 1989-11-22 | 1992-07-21 | Nippon Shokubai Co., Ltd. | Optical material of low specific gravity and excellent impact resistance, optical molding product using the optical material and manufacturing method thereof |
| CA2115587A1 (en) * | 1993-02-18 | 1994-08-19 | Hayato Kihara | Styrene copolymers, polystyrene compositions, processes for producing styrene copolymers, and injection-molded articles |
| JPH0892318A (en) * | 1994-09-22 | 1996-04-09 | Sumitomo Chem Co Ltd | Polystyrene-based resin composition and its production |
| GB9420645D0 (en) * | 1994-10-13 | 1994-11-30 | Dow Chemical Co | Non-linear stytrenic polymer compositions and articles prepared therefrom |
| AU9380198A (en) * | 1997-10-17 | 1999-05-10 | Dow Chemical Company, The | Injection-molded articles made from long chain branched syndiotactic monovinylidene aromatic polymers |
| JP2001521966A (en) * | 1997-10-31 | 2001-11-13 | ザ ダウ ケミカル カンパニー | Rubber-modified monovinylidene aromatic polymer blend |
| TWI226339B (en) * | 1999-03-26 | 2005-01-11 | Shinetsu Chemical Co | High molecular weight compound and the method to prepare the same |
| JP2002037823A (en) * | 2000-07-25 | 2002-02-06 | Kawamura Inst Of Chem Res | Copolymer of styrene dendorimer and olefin and method for producing the same |
| KR100428514B1 (en) * | 2001-11-16 | 2004-04-29 | 금호석유화학 주식회사 | Polymer consisting of linear and nonlinear structure and process for its manufacture by anionic polymerization |
-
2003
- 2003-01-30 CA CA2474454A patent/CA2474454C/en not_active Expired - Lifetime
- 2003-01-30 WO PCT/JP2003/000904 patent/WO2003064524A1/en active Application Filing
- 2003-01-30 US US10/501,920 patent/US7049369B2/en not_active Expired - Lifetime
- 2003-01-30 CN CNB038029499A patent/CN1276936C/en not_active Expired - Lifetime
- 2003-01-30 EP EP03734887A patent/EP1471111B1/en not_active Expired - Lifetime
- 2003-01-30 TW TW092102117A patent/TWI278483B/en not_active IP Right Cessation
- 2003-01-30 KR KR1020047011770A patent/KR100848345B1/en active IP Right Grant
- 2003-01-30 DE DE60335344T patent/DE60335344D1/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8787615B2 (en) | 2003-06-13 | 2014-07-22 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding watermarks |
| US9202256B2 (en) | 2003-06-13 | 2015-12-01 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding watermarks |
| US9191581B2 (en) | 2004-07-02 | 2015-11-17 | The Nielsen Company (Us), Llc | Methods and apparatus for mixing compressed digital bit streams |
| US8972033B2 (en) | 2006-10-11 | 2015-03-03 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding codes in compressed audio data streams |
| US9286903B2 (en) | 2006-10-11 | 2016-03-15 | The Nielsen Company (Us), Llc | Methods and apparatus for embedding codes in compressed audio data streams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1625581A (en) | 2005-06-08 |
| EP1471111A1 (en) | 2004-10-27 |
| US7049369B2 (en) | 2006-05-23 |
| WO2003064524A1 (en) | 2003-08-07 |
| EP1471111A4 (en) | 2006-12-27 |
| TWI278483B (en) | 2007-04-11 |
| US20050038196A1 (en) | 2005-02-17 |
| CA2474454A1 (en) | 2003-08-07 |
| CA2474454C (en) | 2010-08-03 |
| EP1471111B1 (en) | 2010-12-15 |
| DE60335344D1 (en) | 2011-01-27 |
| KR100848345B1 (en) | 2008-07-25 |
| TW200303892A (en) | 2003-09-16 |
| KR20040078148A (en) | 2004-09-08 |
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